Two near-infrared (NIR) emissive π-conjugated covalent organic frameworks (COFs) pTANG1 and pTANG2 are synthesized using Knoevenagel condensation of trioxaazatriangulenetricarbaldehyde (TATANG) with benzene- and biphenyldiacetonitriles, respectively. The morphology of the COFs is affected by the size of TATANG precursor crystals. Donor-acceptor interactions in these COFs result in small bandgaps (≈1.
View Article and Find Full Text PDFUllmann coupling is a widely used reaction for the on-surface growth of low-dimensional carbon nanomaterials. The irreversible nature of this reaction prevents the "self-healing" of defects, and a detailed knowledge of its mechanism is therefore essential to enable the growth of extended ordered structures. However, the dynamics of the Ullmann polymerization remain largely unexplored, as coupling events occur on a timescale faster than conventional scanning probe microscopy imaging frequencies.
View Article and Find Full Text PDFHydrogen-bonded (H-bonded) self-assembly is a suitable approach for tailoring the solid-state packing and properties of organic semiconductors. Here we studied the H-bonded self-assembly of an important class of organic semiconductors, diketopyrrolopyrrole (DPP) derivatives, diselenophenylDPP (DSeDPP), dithiazolylDPP (DTzDPP), and dithienothiophenylDPP (DTTDPP), at solid-liquid interfaces using scanning tunneling microscopy (STM) and density functional theory (DFT). At the 1-octanoic acid/highly ordered pyrolytic graphite (HOPG) interface, DSeDPP and DTzDPP either co-assemble with the solvent H-bonding between lactam and carboxyl groups or form homoassemblies through H-bonding between the lactam groups.
View Article and Find Full Text PDFWe report a rapid, room-temperature mechanochemical synthesis of 2- and 3-dimensional boroxine covalent organic frameworks (COFs), enabled by using trimethylboroxine as a dehydrating additive to overcome the hydrolytic sensitivity of boroxine-based COFs. The resulting COFs display high porosity and crystallinity, with COF-102 being the first example of a mechanochemically prepared 3D COF, exhibiting a surface area of ca. 2,500 m g.
View Article and Find Full Text PDFColloidal quantum dots (QDs) hold great promise as building blocks in solar technologies owing to their remarkable photostability and adjustable properties through the rationale involving size, atomic composition of core and shell, shapes, and surface states. However, most high-performing QDs in solar conversion contain hazardous metal elements, including Cd and Pb, posing significant environmental risks. Here, a comprehensive review of heavy-metal-free colloidal QDs for solar technologies, including photovoltaic (PV) devices, solar-to-chemical fuel conversion, and luminescent solar concentrators (LSCs), is presented.
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